Process of making gasoline



Patented Nov. 21, 1939 2,180,372 rnc'rclrss.` oF MAKING GAsomNn V Bernard Il. Shoemaker, Hammond, Ind., assign- ,l

or to Standard Oil Company,- corporation of Indiana Chicago, lll.,` a

Application necembeu, 193s, serial No. 115,293

2 Claims. This invention relates to the processor making lgasoline, from heavier oils andl more particu-4 larly from'oils of the type known as gas oil wherein the oil is subjected to.cracking and issubsequently separated into gasoline and otherA fractions. One object ofthe invention is to produce a gasoline directly from the cracking proc` ess which does not require sweetening or the removal of mercaptans. Another object of the invention is to provide a process Afor producing a gasoline which has a higher knock rating than' that of cracked gasolines ordinarily produced urider similar lconditions .of crackingtemperatures and pressures. Still another object of the invention is to produce a recycle oil in the 'cracking process which has less tendency to deposit objectionable carbon in the cracking reaction zone and also less tendency to cause corrosion of the cracking equipment, resulting from the presence of sulfur compounds which ordinarily accumulate in said recycle oil. Other objects and advantages of the invention will become' apparent from the following description.

Referring to the drawing which forms a part of this specification, I is a pipe heater typical of those used in cracking operations and I'I is van Y evaporator tower into which the vapors from the heater are injected. A fractionating 'tower I2 is provided for separating the product into gasoline, furnace oil and recycleaoil. Interposed btween the evaporator tower and the fractionating tower are clay treatingl chambers I3 and i4 which are connected in parallel, enabling them to be used a1ternately,'the hot vapors from the evaporator II passing through one of said and thence to said fractionating tower.

As 'an example of the operation ofl my process I mai7 introduce Mid-Continent gas oil by line I5 into heater I0 where it is heated to c high cracking temperature. The temperature in the transfer line I6 passing to the evaporator, for example, may suitably be between 850 :md 1000 F. and a temperature of 900 to 925 F. is usually satisfactory. A quenching liquid may beintroduced into the transfer line preceding the evaporator when it is desired to reduce the vapors.

The Ahot`vapors entering the evaporator pass upward in counterilow to a descending current of reflux liquid introduced by line I'I whereby the temperature is reduced to about .700 to 800 F. and the heavy constituents are condensed and discharged as a tar or fuel oil from the base of the temperature of to 4further reducethe tar in atar strippernot shown-connected by line I8,` from which the distillate fraction is recycled to the cracking coil '39. 'I'he uncondensed vapors are led by line I9 to clay tower I3, valve 20 being closed and valve 2| being open. Clay towers I3 and I4 may 'suitably be clay towers I8. It is usually desirable (Cl. ISG-'28) provided with a perforated screen-'covered false bottom 22 on whichkrests a bed of catalyst in l porous form, permitting the oil vapors to pass downward therethrough and out through line 23 leading to separator 24, valve 25 being open and valve 26 being closed.

Any condensate which collects in separator 24,

including polymeriged higher boiling vhydrocarbons formed from the vapors by the action of the catalyst in chamber I3 is forced by pump 21 through' line I1 to the topof evaporator 'II as `reflux liquid. If the amount of such reux liquid available is insuicient to control the vapor temperature at the top of evaporator I I, additional cooling is supplied by reflux coil 28. However, if the amount .of condensate in separator 24.

accumulates beyond that needed for reux in tower I I, it may be by-passed through valved line 28a leading to the cracking coil 39.

' The vapors from separator 24 are conducted by line -29 to fractionator I2. wherein they are v separated into an overhead vapor fraction comprisinggasoline and gases withdrawn by line 30 to suitable condensingk and stabilizing apparatus not shown. Reilux condensate .formed in frac- "tionator I2 by reflux coil 3I passes downward through the column and collectsI intrap-out plate 32 from which a portion may be withdrawn by` line 33 to sidestripper 34. The bottoms are withdrawn from stripper 34 by line 35 and form kerosene or furnace oilone of the desiredproducts of the process.

The remaining reflux liquid passes down through column I2 where it is subjected'to reboiling by coil 36 and thence is `conducted by line 3'I and pump 38 to an intermediate point of the pipe heater coil 39 where it is further cracked by the high temperature prevailing therein.

` In commencing the operation of the process it is desirable to preliminarily heat `the catalyst in towers I3 and I4 to the desired catalyst treating temperature, i. e., '700 to 750 F. and this may 'be conveniently accomplished by the introduction of superheated steam through lines 40 and 4I, the steam being withdrawn from the catalyst chambers by lines 42 and 43 and either vented to the atmosphere by vent 44 or condensed in coil 45 leading to separator 46 from which condensed water is withdrawn by line 41.

When the catalyst becomes spent or vloses a large part of its eiiiciency in the catalyst chamber which is in operation, the hot vapors from evaporator II are diverted to the other catalyst chamber and the spent catalyst is regeneratedor "replaced by fresh catalyst. If it is regenerated through lines 40 or 4I as before to remove as `much volatile hydrocarbon material as possible. `Referring to catalyst chamber I3, valves 25 and -2l are closed during this operation and the steam and volatilized hydrocarbons are withdrawn through line 42 to condenser 45 and separator 46 where hydrocarbon collects and is withdrawn by line 48 leading to separator- 214. After the hy- 42 is closed and vent 44 is opened and at the same time a current of preheated air is introduced by valved line l; the air coming in contact y with the catalyst produces a combustion of the residual organic material and carbon deposited thereon and the rate of combustion is controlled by regulating the amount of steam introduced by line 40 at the sainetime. After combustion is complete the catalyst chamber is thoroughly steamed out to remove any air contained in it and the catalyst is then ready for treating more hydrocarbon vapor.

If desired, the catalyst may be removed by manways 5l and 52 and regenerated in a separate apparatus.

One of the unique features'of my process is the control of the temperature'in the catalyst chambers within the critical range for satisfactory treating. I have found temperatures below 700 F. are ineffective for producing the desired results of sweetening and increasing knock rat.- ing of the final gasoline distillate. Temperatures above 800 F. are likewisf\ undesirable in that excessive coking of hydrocarbons occurs on the surface of the catalyst, with the result that the catalyst life is so short as to make the process entirely uneconomical, and I prefer to maintain the catalyst temperature below '150 F. The temperature of the catalyst towers is most conveniently regulated by controlling the reflux on tower Il and thus controlling the temperature of the incoming vapor. The sweetenlng effect of the catalyst appears to be brought about by decomposition of the mercaptans with the formation of hydrogen sulfide which may be removed from the gasoline along with other gases in the stabilizer or may be absorbed by a. suitable alkali such as sodium hydroxide solution. Accordingly, I obtain a desulfurization of the gasoline in additionto sweetening.

The effect of th catalyst on improving the knock rating of the gasoline is shown in the following table where the knock rating is ex' pressed as octane number improvement. The gasoline without the catalyst treatment possessed an octane number of 65.5. Several diiferent catalysts were employed as indicated in the table.

Total Knock Yield of Temyield rating sweet Catalyst perbblsJton imgrv. gasoline A me 0:-l c. .R (nba/mn catalyst motor of catalyst) r 0F. Fullers earth (F1orida)-- 15o i017 2. 1 4.83 Fullers earth (Dlinois) 750 684 l. 9 300 Bruni 75o 1420 0.5 1303 Lime o son 0.o aas The brucite is a natural magnesia hydrate.

Yields given are the amount of gasoline throughput before revivifying the catalyst.

The pressure employed in my process may vary considerably, but it is desirable to conduct the operation at a pressure between 100 and 400 pounds per square inch. Pressures as high as 750 pounds may be used but in that case it is desirable to reduce the pressure at the transfer line and/or between the evaporator and the catalyst chamber by a suitable pressure reducing valve. If desired, I may also operate the heater higher knock rating gasoline.

and evaporator at a pressure of about 100 to 400 pounds per square inch and operate the catalyst chamber at atmospheric pressure. By operating the catalyst chambers at the same pressure as drocarbon has been steamed'out, va1ve49 in line vby increased, requiring less revivication.

The catalyst in my process is believed to have no effect on the cracking of the hydrocarbons per se inasmuch as cracking is always accompanied by deposition of coke which rapidly destroys catalytic action. The effect of the catalyst at the temperatures which I employ is apparently due to the combined action on the sulfur compounds contained in the hydrocarbon vapors and to the molecular rearrangement of some unsaturated molecules. It has been found, for example, that certain sulfur compounds, particularly mercaptan's, sulides and dsuliides have an adverse effect upon the knock rating of the gasoline and it appears that the present process removes certain of these undesirable sulfur compounds by converting them into hydrocarbons and hydrogen sulfide. This is supported by the fact that mercaptans are removed from alarge part of the gasoline.

I have found that the 'higher boiling sulfur compounds are most diflicult to decompose by the action of a catalyst and one of the advantages of my process is the separation of such high boiling sulfur compounds in separator 24 and fractionator I2 combined with recycling these high boiling sulfur compounds back to the heater Il! and evaporator Il whence they are again returned to the catalyst chamber for repeated treatment. In this manner I have found it possible to remove a larger proportion of those sulfur compounds which have an adverse effect on the knock rating of the gasoline.

Although I have described the process with regard to certain specific operations it should be understood that my process may be employed in various other ways with other hydrocarbon materials. For example, instead of gas oil I may employ as a feed stock a heavy naphtha of low knock rating, e. g., 45 octane number, in which case the operation will consist of reforming the f low knock rating heavy naphtha to produce In this case the gasoline content` of the vapors entering the catalyst chambers I3 and I4 will be considerably higher than in the case where gas oil is the charging stock to the process. When charging gas oil, for example, the vapors entering the catalyst chamber will usually contain not more than 25 to 40% of gasoline. A typical analysis of these vapors is as follows:

9% at 158 F.

' 25% at 400 F. 90% at 600 F. MaX. 700 F.

It will be noted from this distillation that these vapors contained about 25% lof gasoline and therefore about '75% of vapor treated in the clay chambers is separated and recycled in the process.

Although I have described specic catalysts such as Florida and Illinois fullers earth, it should be understood that I may use any of the well-known argillaceous catalytic materials, including bentonite, Death Valley clay, acid treated clays, bauxite, etc. It is desirable, however, that argillaceous earth at a. temperature between 700 l and 800 F., thereafter conducting the vapors to a fractionating zone, therein separating gasoline from unconverted heavy oil and recycling saidunconverted heavy oil, consisting of about 60% to. 75% of the charging stock, to said 'cracking step. v

2. The process of claim 1 wherein the pressure of the vapors in the catalytic mass is maintained between about 100 and 400 inch.

' BERNARD H. SHOEMAKER.

pounds per square ,10 

